EP0616005A1 - Nicht-vernetzte Polyethylen Teilchen, die Herstellung geschäumter Teilchen und nicht vernetzte, geschäumte Teilchen - Google Patents

Nicht-vernetzte Polyethylen Teilchen, die Herstellung geschäumter Teilchen und nicht vernetzte, geschäumte Teilchen Download PDF

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EP0616005A1
EP0616005A1 EP94103755A EP94103755A EP0616005A1 EP 0616005 A1 EP0616005 A1 EP 0616005A1 EP 94103755 A EP94103755 A EP 94103755A EP 94103755 A EP94103755 A EP 94103755A EP 0616005 A1 EP0616005 A1 EP 0616005A1
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particles
uncrosslinked
polyethylene
resin
resin particles
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French (fr)
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EP0616005B1 (de
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Hisao Tokoro
Kazuo Tsurugai
Hidehiro Sasaki
Masaharu Oikawa
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JSP Corp
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JSP Corp
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
    • C08L23/0815—Copolymers of ethene with aliphatic 1-olefins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/16—Making expandable particles
    • C08J9/18—Making expandable particles by impregnating polymer particles with the blowing agent
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/04—Homopolymers or copolymers of ethene
    • C08J2323/06—Polyethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/06—Polyethene

Definitions

  • the present invention relates to uncrosslinked polyethylene particles to be expanded and uncrosslinked polyethylene expanded particles obtained therefrom.
  • LLDPE uncrosslinked straight-chain low-density polyethylene
  • LLDPE expanded particles capable of being molded without specifically giving an internal pressure
  • the applicant suggested a method wherein use is made of, as raw material resin particles of expanded particles, LLDPE particles having a crystalline structure in which a double peak appears in the DSC curve so that LLDPE expanded particles having a double peak in the DSC curve can be obtained securely (Japanese Patent Application Laid-Open No. 43206/1990).
  • novel uncrosslinked LLDPE particles wherein, in the DSC curve of the resin particles, there is a specific relationship between the quantity of heat absorbed in the range from 50 °C to (the melting point - 10) °C and the total quantity of heat absorbed in the range from 50 °C to the temperature at which the melting is completed and the temperature width at 1/2 of the peak height of the endothermic peak whose apex is located on the side of the temperature higher than 115 °C is 5 °C or more, leading to the completion of the present invention.
  • the present resin particles are resin particles for the production of expanded particles whose base resin is an uncrosslinked polyethylene, wherein the uncrosslinked polyethylene that is the base resin of said resin particles has a density of over 0.920 g/cm3 and up to and including 0.940 g/cm3, and in the DCS curve of said resin particles that is obtained by using a differential scanning calorimeter in such a manner that after 1 to 10 mg of the resin particles is heated to 200 °C at 10 °C/min and then is cooled to 40 °C at 10 °C/min, heating is again carried out to 200 °C at 10 °C/min and during the second heating the measurement for the DSC curve is carried out, q1/q total ⁇ 0.5 wherein q1 stands for the quantity of heat absorbed in the range of the DSC curve of from 50 °C to (the melting point - 10) °C in terms of J/g and q total stands for the total quantity of absorbed heat of the DSC curve of from 50 °C to the temperature
  • the present expanded resin particles are expanded particles that are obtained by dispersing resin particles impregnated with an expanding agent into a dispersing medium in a closed vessel and releasing the resin particles and the dispersing medium from the closed vessel at the softening temperature of the resin particles or a temperature higher than that into a low-pressure region, wherein the base resin of the resin particles is an uncrosslinked polyethylene having a density of over 0.920 g/cm3 and up to and including 0.940 g/cm3, and said resin particles are such uncrosslinked polyethylene particles that, in the DCS curve of said resin particles that is obtained by using a differential scanning calorimeter in such a manner that after 1 to 10 mg of the resin particles is heated to 200 °C at 10 °C/min and then is cooled to 40 °C at 10 °C/min, heating is again carried out to 200 °C at 10 °C/min and during the second heating the measurement for the DSC curve is carried out, q1/q total ⁇ 0.5, wherein q1
  • the quantity q1 of heat absorbed in the range of from 50 o C to (the melting point - 10) °C is the quantity of absorbed heat of the part that is surrounded by the line b connecting the point at the temperature of 50 °C on the DSC curve to the point of the temperature at which the melting is completed on the DSC curve and the DSC curve and is on the side of the temperature lower than ⁇ the melting point (that is the temperature of the apex of the peak, that apex being on the side of the temperature higher than 115 °C, i.e. the temperature at the intersection point a of the tangent line d and the tangent line e as shown in Fig. 1) - 10 °C ⁇ .
  • q total is the total quantity of absorbed heat of the DSC curve from 50 °C to the temperature at which the melting is completed and is the quantity of absorbed heat corresponding to the part surrounded by the line b and the DSC curve shown in Fig. 1.
  • the quantity of heat absorbed q total when melted is 90 J/g or more.
  • the length of the segment ac is designated as the peak height h. Further, if there is only one endothermic peak in the DSC curve and the temperature of the apex of said endothermic peak is 115 °C or higher, for said endothermic peak the peak height h is found in the same way as above. Further, as is shown in Fig.
  • the tangent line that is tangent to the higher temperature side of the highest-temperature side peak out of the endothermic peaks wherein the temperature of the apexes is 115 °C or higher and whose gradient is largest i.e. the tangent line d and the tangent line that is tangent to the low-temperature side of the lowest-temperature side peak out of the endothermic peaks wherein the temperature of the apexes is 115 °C or higher and whose gradient is largest in terms of absolute value, i.e. the tangent line e are drawn.
  • the peak height h is found in the same way as above, except that the intersection point of these tangent lines is designated as a.
  • the temperature width w at 1/2 of the peak height h of the endothermic peak wherein the temperature of the apex is 115 °C or higher (hereinafter referred to as the half width of the endothermic peak) is the length of the part of the line segment that is passed through the mid point of the peak height h, is parallel to the line b, and is located between the tangent line d and the tangent line e.
  • the half width w of the above endothermic peak is 5 °C or more and if the half width of the endothermic peak is less than 5 °C, because the proper expanding temperature range is narrow so that it is difficult to prevent the energy of the endothermic peak on the higher temperature side of expanded particles from varying, it is difficult to obtain preexpanded particles good in moldability in a mold.
  • the uncrosslinked polyethylene particles of the present invention has an MI of 0.1 to 5 g/10 min, particularly 0.5 to 3 g/10 min.
  • the uncrosslinked polyethylene particles of the present invention has an MI of 0.8 g/10 min or over but less than 2.0 g/10 min and/or a melting point of over 120 °C. If the MI is less than 0.8 g/10 min and/or the melting point is less than 120 °C or below, the effect of improving the expansion rate is not remarkable and if the MI is 2.0 g/10 min or over, the rate of the closed cells is liable to be down.
  • the uncrosslinked polyethylene particles wherein the n-hexane extract is 0.3 to 1.5 % are preferable because they are excellent in expandability and can produce expanded particles high in cell strength. It is essential that the uncrosslinked polyethylene constituting the present resin particles has a density of over 0.920 g/cm3 and up to and including 0.940 g/cm3. If the density is 0.920 g/cm3 or below, the expanded particles or the molded product is liable to shrink while if the density is over 0.940 g/cm3, the proper expanding temperature range at the time of expanding is not very wide.
  • LLDPE and a mixture of LLDPE and other polyethylene can be mentioned.
  • the above properties in the DSC curve can be obtained, for example, in such a manner that (1) when LLDPE that is obtained as a copolymer of ethylene and an ⁇ -olefin is produced, a catalyst or polymerization conditions are selected to make nonuniform the distribution of the ethylene and the ⁇ -olefin in the LLDPE or (2) ordinary LLDPE's different from each other in melting point and/or density are mixed or LLDPE is mixed with low-density polyethylene (hereinafter referred to as LDPE) or high-density polyethylene (hereinafter referred to as HDPE).
  • LDPE low-density polyethylene
  • HDPE high-density polyethylene
  • ⁇ -olefin having 4 to 10 carbon atoms that constitutes the above LLDPE for example, 1-butene, 1-pentene, 1-hexene, 3,3-dimethyl-1-butene, 4-methyl-1-pentene, 4,4-dimethyl-1-pentene, and 1-octene can be mentioned.
  • the content of these ⁇ -olefins in the LLDPE is preferably 1 to 20 % by weight, particularly preferably 3 to 10 % by weight. If the content of ⁇ -olefins in the LLDPE exceeds 20 % by weight, in some cases the strength, for example, against bending or compression is liable to be down.
  • the densities of the LLDPE's are preferably selected such that if the density of one of the LLDPE's is designated as d (g/cm3), the density of at least one of the other LLDPE's is d + 0.005 (g/cm3) or over and preferably the difference in melting point is 5 to 15 °C.
  • d density of one of the LLDPE's
  • d density of at least one of the other LLDPE's
  • the difference in melting point is 5 to 15 °C.
  • the density and the melting point of the LLDPE are selected to be d + 0.02 (g/cm3) or over and T + 10 to T + 20 (°C) respectively.
  • an LLDPE is used as a major component and other LLDPE different from the former LLDPE in density or in melting point or other polyethylene such as LDPE and HDPE is mixed therewith by a conventional known method such as the dryblending method and the master batch method.
  • the mixing ratio is preferably such that to 100 parts by weight of one LLDPE, 20 to 60 parts by weight of the other LLDPE or 2 to 30 parts by weight of HDPE is mixed and further as a third component 10 parts by weight or less of LDPE can be added thereto.
  • the resins to be mixed have an MI of 0.5 to 3 g/10 min and further if the LLDPE that is a major component has an MI of m (g/10 min), preferably the resins to be mixed have an MI of m ⁇ 2 (g/10 min).
  • the base resin a mixture of polyethylene resins is used, it is preferable that an LLDPE having a density of 0.925 g/cm3 or less is mixed as one component, because the adjustment of the present resin particles becomes easy.
  • the process of adjusting the resin to obtain the intended pattern of the DSC curve can be simplified. That is, when resins different from each other in property are mixed to obtain a resin mixture different from the original resins in property, the shape of the DSC curve of the resin mixture has a peak height approximately in proportion to the mixing ratio of the original resins and is approximately similar to the shape obtained by superimposing the shapes of the DSC curves of the original resins.
  • a resin 1 and a resin 2 whose difference in melting point is 5 °C or over are selected to secure w ⁇ 0.5 (°C) and a resin 3 whose DSC curve has a broad wing on the low-temperature side and shows a great quantity of heat absorbed on the low-temperature side is selected to secure q1/q total ⁇ 0.5 and these resins are mixed such in a suitable ratio that the heights of the peaks are brought near to the peak height of the DSC curve of the intended resin mixture.
  • the present resin particles can also be adjusted by mixing two kinds of resins.
  • the resin particles of the present invention can be adjusted not only by mixing the above two kinds of resins or three kinds of resins but also by mixing a number of resins.
  • the present resin particles are obtained in such a manner that the resins obtained in the above adjusting method are finally subject to DSC and further selection is made based on the results of the measurement.
  • an inorganic material can be incorporated if required.
  • an inorganic hydroxide such as aluminum hydroxide, calcium hydroxide, and magnesium hydroxide
  • an inorganic carbonate such as calcium carbonate, magnesium carbonate, and barium carbonate
  • an inorganic sulfite such as calcium sulfite and magnesium sulfite
  • an inorganic sulfate such as calcium sulfate, aluminum sulfate, manganese sulfate, and nickel sulfate
  • an inorganic oxide such as calcium oxide, aluminum oxide, and silicon oxide
  • an inorganic chloride such as sodium chloride, magnesium chloride, and calcium chloride
  • a natural mineral such as borax, talc, clay, kaolin, and zeolite
  • the above inorganic materials can be used singly or as a mixture of two or more and may be mixed with the melted resin in an extruder from which the melted resin will be extruded into pellets.
  • the inorganic material is added generally in the form of powder and there are no particular restrictions on the inorganic material if the particle diameter falls within a range that is generally used. However it is preferable that the particle diameter is generally 0.1 to 100 ⁇ m, particularly 1 to 15 ⁇ m.
  • the content of the inorganic material in the resin particles is 0.001 to 5 % by weight and particularly in the case wherein the inorganic material is talc, the content is preferably 0.003 to 0.5 % by weight while in the case of borax, aluminum hydroxide, or zeolite, the content is preferably 0.1 to 2 % by weight.
  • the resin particles containing an inorganic material have generally a particle diameter of 0.3 to 5 mm, particularly 0.5 to 3 mm.
  • the dispersing medium in which the resin particles will be dispersed are those that do not dissolve the resin particles, such as water, ethylene glycol, glycerin, methanol, and ethanol, and generally water is used as the dispersing medium.
  • the process wherein the resin particles are impregnated with an expanding agent may be carried out before or after the process wherein the resin particles are dispersed in a dispersing medium in a closed vessel, but generally is carried out simultaneously with the process wherein the resin particles are dispersed.
  • the expanding agent is once dissolved or dispersed in the dispersing medium and then is impregnated into the resin particles, so that the expanding agent can be impregnated into the resin particles, for example, in such a manner that the resin particles, the expanding agent, and the dispersing medium are placed in a closed vessel and are heated or placed under pressure with stirring.
  • the expanding agent used in the production of the present expanded particles may be any of volatile expanding agents, such as propane, butane, pentane, hexane, cyclobutane, cyclohexane, trichlorofluoromethane, and dichlorodifluoromethane, and inorganic gas expanding agents, such as nitrogen, carbon dioxide, argon, and air, with particular preference given to carbon dioxide or a mixture of carbon dioxide with a volatile expanding agent.
  • volatile expanding agents such as propane, butane, pentane, hexane, cyclobutane, cyclohexane, trichlorofluoromethane, and dichlorodifluoromethane
  • inorganic gas expanding agents such as nitrogen, carbon dioxide, argon, and air, with particular preference given to carbon dioxide or a mixture of carbon dioxide with a volatile expanding agent.
  • the above inorganic gas expanding agent or a mixture of the above inorganic gas expanding agent with the above volatile expanding agent is
  • a fusion preventive agent for preventing the resin particles from being fused can be used.
  • the fusion preventive agent any of inorganic fusion preventive agents or organic fusion preventive agents that do not dissolve in the dispersing medium such as water and will not be melted by heating can be used and generally an inorganic fusion preventive agent is preferable.
  • an inorganic fusion preventive agent for example, aluminum oxide, titanium oxide, aluminum hydroxide, basic magnesium carbonate, basic zinc carbonate, calcium carbonate, calcium phosphate, magnesium pyrophosphate, and talc can be mentioned.
  • the above fusion preventive agent has a particle diameter of 0.001 to 100 ⁇ m, particularly 0.001 to 30 ⁇ m.
  • the amount of the fusion preventive agent to be added is generally 0.01 to 10 parts by weight per 100 parts by weight of the resin particles.
  • an emulsifying agent can also be added.
  • an anionic surface-active agent such as sodium dodecylbenzenesulfonate and sodium oleate, is preferable.
  • the emulsifying agent is added generally in an amount of 0.001 to 5 parts by weight per 100 parts by weight of the resin particles.
  • the expanding temperature is a temperature equal to or above the softening temperature of the resin particles and preferably is a temperature near the melting point of the resin particles, particularly preferably a temperature in the range of from (the melting point - 10 °C) or over to (the melting point + 5 °C) or below.
  • the quantity of heat absorbed on the high-temperature side is 10 J/g or more.
  • the expanding temperature is preferably a temperature in the range of from (the melting point - 15 °C) or over to (the melting point + 10 °C) or below, particularly from (the melting point - 10 °C) or over to (the melting point + 5 °C) or below.
  • the heating rate at the heating to the expanding temperature is preferably 1 to 10 °C/min, particularly 2 to 5 °C/min.
  • the pressure of the atmosphere into which the expandable resin particles and the dispersing medium are discharged from the closed vessel may be a pressure lower than the pressure in the vessel and is generally equal to the atmospheric pressure.
  • the temperature of the atmosphere into which the discharge is carried out is generally equal to normal temperatures, but when the temperature of that atmosphere is increased to 60 to 110 °C, preferably 80 to 100 °C, by heating with a heating medium, such as steam, in comparison with the case wherein the discharge is carried out into an atmosphere having normal temperatures, the expansion rate of the expanded particles is increased about 1.5 to 2.0 times and an effect of increasing the cell diameter is obtained in association therewith, resulting in good moldability.
  • Fig. 1 is an explanatory diagram showing the DSC curve of the present uncrosslinked polyethylene particles for the production of expanded particles.
  • Fig. 2 is an explanatory diagram showing the DSC curve of the present uncrosslinked polyethylene particles for the production of expanded particles, the shape of the DSC curve being different from that of the DSC curve in Fig. 1.
  • Fig. 3 is an explanatory diagram showing the DSC curve of the present uncrosslinked polyethylene resin particles for the production of expanded particles and the DSC curves of the raw material resins used for adjusting that resin particles.
  • Fig. 4 shows the DSC curve obtained in the second heating of Resin A used in Examples 1 and 2.
  • Fig. 5 shows the DSC curve obtained in the second heating of Resin B used in Example 3.
  • Fig. 6 shows the DSC curve obtained in the second heating of Resin C used in Comparative Example 1.
  • Fig. 7 shows the DSC curve obtained in the second heating of Resin D used in Comparative Example 2.
  • Fig. 8 shows the DSC curve obtained in the second heating of Resin E used in Comparative Example 3.
  • Fig. 9 shows the DSC curve obtained in the second heating of Resin F used in Comparative Example 4.
  • Fig. 10 shows the DSC curve obtained in the second heating of Resin G used in Comparative Example 5.
  • Fig. 11 shows the DSC curve obtained in the second heating of Resin H used in Comparative Example 6.
  • Fig. 12 shows the DSC curve obtained in the second heating of Resin I used in Comparative Examples 7 and 8.
  • Fig. 13 shows the DSC curve obtained in the second heating of Resin Mixture a used in Examples 4 and 7 to 9.
  • Fig. 14 shows the DSC curve obtained in the second heating of Resin Mixture b used in Example 5.
  • Fig. 15 shows the DSC curve obtained in the second heating of Resin Mixture c used in Example 6.
  • Fig. 16 shows the DSC curve obtained in the second heating of Resin Mixture d used in Comparative Example 9.
  • Fig. 17 shows the DSC curve obtained in the second heating of Resin Mixture e used in Comparative Example 10.
  • Fig. 18 shows the DSC curve obtained in the second heating of Resin Mixture f used in Comparative Example 11.
  • Fig. 19 shows the DSC curve obtained in the second heating of Resin J.
  • Fig. 20 shows the DSC curve obtained in the second heating of Resin K.
  • Fig. 21 shows the DSC curve obtained in the second heating of Resin L.
  • Resins A to I shown in Table 1 were melted in an extruder and was extruded from a die into strands and the strands were quenched in water and cut into pellets each having a weight of about 4 mg.
  • a differential scanning calorimeter After the pellets were heated at a rate of 10 °C/min to 200 °C and then were cooled to room temperature at 10 °C/min, heating was again carried out at a rate of 10 °C/min to 200 °C and during the second heating the measurement for the DSC curve was carried out, the DSC curves being shown in Figs. 4 to 12.
  • the expanded particles were obtained in such a manner that, as an expanding agent, carbon dioxide or a mixture of carbon dioxide and isobutane was used, 4 g of mica as a dispersant, 0.4 g of sodium dodecylbenzenesulfonate as an emulsifier, and 3 l of water per 100 g of the resin particles were blended in a closed vessel (having a volume of 5 liters), then after they were heated with stirring to the expanding temperature shown in Table 2 without heating to a temperature equal to or over the melting completion temperature of the resin and were kept at the expanding temperature for 15 min, a carbon dioxide back pressure equal to the equilibrium vapor pressure, and with that pressure retained, one end of the vessel is released to discharge the resin particles and the water simultaneously to allow the resin particles to expand.
  • the average bulk expansion rate of the obtained expanded particles and the moldability of the expanded particles are also shown in Table 2.
  • the measurement of the DSC of the respective expanded particles was carried out and the quantities of the heat absorbed on the high-temperature side were determined and are also shown in Table 2. Further, with respect to the expanded particles, the quantities of the heat absorbed on the high-temperature side can be measured by a conventionally known method (e.g., a method described in U.S. Patent No. 4,948,817).
  • Examples 1 to 3 were repeated, except that resin mixtures a to f obtained by mixing (dryblending) two or three kinds of resins selected from the resins shown in Table 1 in ratios per 100 g of the resin mixture shown in Table 3.
  • the resin mixture particles were subjected to DSC and the DSC curves obtained in the second heating are shown in Figs. 13 to 18 (incidentally, the DSC curves of the individual Resins J, K, and L used in the mixing that were obtained in the second heating are shown in Figs. 19 to 21 respectively).
  • the DSC curves of Resin Mixtures a to f correspond to Figs. 13 to 18 respectively.
  • Example 7 to produce expanded particles, Example 8 was repeated, except that when the expandable resin particles and the water were simultaneously discharged from the closed vessel to allow the resin particles to expand, the discharge pipe was heated with steam having a temperature of 100 °C, in Example 8, to produce expanded particles, Example 4 was repeated, except that the expanding agent was changed to carbon dioxide, and in Example 9, to produce expanded particles, Example 7 was repeated, except that 0.2 % by weight of borax was added to the resin particles.
  • the average bulk expansion rate of the respective expanded particles and the moldability were evaluated and are shown in Table 5.
  • the obtained expanded particles were subjected to DSC to find the quantities of heat absorbed on the high-temperature side, which are also shown in Table 5.
  • the shrinkage of the molded product in the direction of the surface was measured and the evaluation was made based on the following criteria: O: the shrinkage in the direction of the surface was less than 2.5 %. ⁇ : the shrinkage in the direction of the surface was 2.5 % or higher but less than 3 %. ⁇ : the shrinkage in the direction of the surface was 3 % or higher but less than 4 %. x: the shrinkage in the direction of the surface was 4 % or over.
  • the evaluation was made based on the following criteria: O: the breakage of the material in the fracture was 75 % or over. ⁇ : the breakage of the material in the fracture was 65 % or more but less than 75 %. ⁇ : the breakage of the material in the fracture was 40 % or more but less than 60 %. x : the breakage of the material in the fracture was less than 40 %.
  • the present uncrosslinked polyethylene particles for the production of expanded particles have a density of over 0.920 g/cm3 and up to and including 0.940 g/cm3 and, in the DSC curve of the resin particles, there is such a relationship q1/q total ⁇ 0.5 and the temperature width at 1/2 of the height of the endothermic peak the temperature of the apex of which is 115 °C or over is 5 °C or more, expanded particles excellent in moldability and having a high expansion rate can be produced securely, and since the expanding efficiency is excellent, expanded particles having a high expansion rate can be obtained by using a smaller amount of an expanding agent, and therefore there is an effect enabling to reduce the amount of an expanding agent to be used.
  • expanded particles having a high expansion rate can be easily obtained even by using an inexpensive inorganic gas expanding agent such as carbon dioxide, expanding agents that are hitherto used and are likely to destroy the environment, such as halogenated hydrocarbons and other petroleum gases, can be replaced with the inorganic gas expanding agents, the cost of expanding agents can be reduced, and since equipments for recovering expanding agents and the operation for recovering expanding agents as in the case wherein expanding agents that are likely to destroy the environment are used are not required, the cost can be decreased considerably.
  • the expanded particles obtained by using the present resin particles can produce a good molded product without applying a special internal pressure, a temperature range suitable for molding is widened, and in particular, molding at a low molding temperature in comparison with the prior art becomes possible.
  • the secondary expansion and the fusion of the expanded particles becomes good, the moldability of the expanded particles is improved considerably, with the result that the molded product is prevented, for example, from shrinking thereby improving the dimensional accuracy, and further the cost of the production of the obtainable molded product can be drastically decreased, for example, because of a decrease in scrap of the molded product or a saving in energy for molding due to a low molding temperature.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
EP94103755A 1993-03-17 1994-03-11 Nicht-vernetzte Polyethylen Teilchen, die Herstellung geschäumter Teilchen und nicht vernetzte, geschäumte Teilchen Expired - Lifetime EP0616005B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP82676/93 1993-03-17
JP08267693A JP3279382B2 (ja) 1993-03-17 1993-03-17 無架橋ポリエチレン系樹脂発泡粒子及びその製造方法

Publications (2)

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EP0616005A1 true EP0616005A1 (de) 1994-09-21
EP0616005B1 EP0616005B1 (de) 1998-02-18

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EP94103755A Expired - Lifetime EP0616005B1 (de) 1993-03-17 1994-03-11 Nicht-vernetzte Polyethylen Teilchen, die Herstellung geschäumter Teilchen und nicht vernetzte, geschäumte Teilchen

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US (1) US5459169A (de)
EP (1) EP0616005B1 (de)
JP (1) JP3279382B2 (de)
KR (1) KR0133478B1 (de)
CA (1) CA2118851A1 (de)
DE (1) DE69408548T2 (de)
TW (1) TW307784B (de)

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EP0687709A1 (de) * 1994-06-13 1995-12-20 Basf Aktiengesellschaft Polyolefin-Partikelschaum
EP0924244A2 (de) * 1997-12-15 1999-06-23 Kaneka Corporation Vorgeschäumte Teilchen aus unvernetztem linearen Polyethylen mit niedriger Dichte
DE19681650B4 (de) * 1995-11-15 2005-07-14 Asahi Kasei Kabushiki Kaisha Vorexpandierte Polyethylenkügelchen und Verfahren zu ihrer Herstellung
WO2020000336A1 (en) * 2018-06-29 2020-01-02 Dow Global Technologies Llc Compositions suitable for manufacturing polyethylene foam, and articles thereof

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KR0159801B1 (ko) * 1994-08-06 1999-01-15 박원배 폴리올레핀계 수지의 미세 셀 예비 발포체 및 그의 제조 방법
JP4083807B2 (ja) 1996-08-12 2008-04-30 株式会社ジェイエスピー 自動車バンパー芯材
US6133331A (en) * 1996-12-13 2000-10-17 Jsp Corporation Expanded particles of polyolefin resin and process for preparing the same
US5883141A (en) * 1997-03-25 1999-03-16 Kaneka Corporation Process for preparing polyolefin resin pre-expanded particles
US6818161B2 (en) 1997-04-01 2004-11-16 Jsp Corporation Molded body of thermoplastic resin having sound absorption characteristics
TW369475B (en) 1997-06-18 1999-09-11 Jsp Corp Production apparatus of expansion-molded article, auxiliary member for transfer of foamed particles and production method of expansion-molded article
DE19739113A1 (de) * 1997-09-06 1999-03-11 Gefinex Polymerschaeume Gmbh Vorexpandierte polyolefinische Schaumpartikel
JP4111417B2 (ja) 1997-12-01 2008-07-02 株式会社ジェイエスピー ポリプロピレン系樹脂発泡粒子及び型内成型体
JP3692760B2 (ja) * 1998-01-30 2005-09-07 株式会社カネカ ポリプロピレン系樹脂型内発泡成形体の製造方法
MY114837A (en) * 1998-03-23 2003-01-31 Jsp Corp Foamed and expanded beads of polypropylene resin for molding
EP0963827B1 (de) * 1998-06-11 2002-10-23 Jsp Corporation Geformter Gegenstand aus geschäumten und expandierten Propylenperlen
JP3950557B2 (ja) 1998-07-30 2007-08-01 株式会社カネカ ポリプロピレン系樹脂予備発泡粒子およびそれからの型内発泡成形体の製造方法
KR20020055589A (ko) 1999-12-28 2002-07-09 다케다 마사토시 발포성 폴리스티렌계 수지입자 및 이를 이용한 발포체
US20060165972A1 (en) * 2005-01-27 2006-07-27 Chimelak Robert R Lightweight, high-strength load bearing floor structure
EP2524941B1 (de) * 2010-01-15 2019-05-15 Kaneka Corporation Expandiertes partikel aus polyethylenbasiertem harz und in der form expandierter artikel aus polyethylenbasiertem harz
US8936072B2 (en) 2010-06-11 2015-01-20 Hewlett-Packard Development Company, L.P. Thermal distribution systems and methods
JP6005404B2 (ja) * 2012-05-30 2016-10-12 ポリマテック・ジャパン株式会社 粘性流体封入ダンパーおよび防振性組成物
CN105218850B (zh) * 2014-06-06 2019-06-28 茂泰(福建)鞋材有限公司 一种高弹热塑性聚氨酯发泡粒子及其成型体的制备方法
DE202019003339U1 (de) * 2019-08-12 2020-11-13 Walter Kunststoffe Gmbh Compound-Additiv für thermoplastische Kunststoffe
JP7130080B1 (ja) 2021-03-15 2022-09-02 株式会社ジェイエスピー ポリエチレン系樹脂発泡粒子、ポリエチレン系樹脂発泡粒子の製造方法

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EP0113903A2 (de) * 1982-12-20 1984-07-25 Japan Styrene Paper Corporation Verfahren zur Herstellung von vorgeschäumten Polymerpartikeln
EP0123816A1 (de) * 1983-04-05 1984-11-07 Kanegafuchi Kagaku Kogyo Kabushiki Kaisha Vorgeschäumte Polyolefinperlen und Verfahren zu ihrer Herstellung
EP0279455A2 (de) * 1987-02-20 1988-08-24 Kanegafuchi Kagaku Kogyo Kabushiki Kaisha Verfahren zur Herstellung von Schaumstoffkörpern aus linearem Polyäthylen mit niedriger Dichte
EP0296438A2 (de) * 1987-06-23 1988-12-28 Japan Styrene Paper Corporation Vorgeschäumte Teilchen aus unverzweigtem LLPDE und Verfahren zu deren Herstellung
EP0359907A2 (de) * 1988-09-21 1990-03-28 Kohjin Co., Ltd. Verfahren zur Herstellung von heissschrumpfbaren Polyethylen-Folien

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EP0113903A2 (de) * 1982-12-20 1984-07-25 Japan Styrene Paper Corporation Verfahren zur Herstellung von vorgeschäumten Polymerpartikeln
EP0123816A1 (de) * 1983-04-05 1984-11-07 Kanegafuchi Kagaku Kogyo Kabushiki Kaisha Vorgeschäumte Polyolefinperlen und Verfahren zu ihrer Herstellung
EP0279455A2 (de) * 1987-02-20 1988-08-24 Kanegafuchi Kagaku Kogyo Kabushiki Kaisha Verfahren zur Herstellung von Schaumstoffkörpern aus linearem Polyäthylen mit niedriger Dichte
EP0296438A2 (de) * 1987-06-23 1988-12-28 Japan Styrene Paper Corporation Vorgeschäumte Teilchen aus unverzweigtem LLPDE und Verfahren zu deren Herstellung
EP0359907A2 (de) * 1988-09-21 1990-03-28 Kohjin Co., Ltd. Verfahren zur Herstellung von heissschrumpfbaren Polyethylen-Folien

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0687709A1 (de) * 1994-06-13 1995-12-20 Basf Aktiengesellschaft Polyolefin-Partikelschaum
DE19681650B4 (de) * 1995-11-15 2005-07-14 Asahi Kasei Kabushiki Kaisha Vorexpandierte Polyethylenkügelchen und Verfahren zu ihrer Herstellung
EP0924244A2 (de) * 1997-12-15 1999-06-23 Kaneka Corporation Vorgeschäumte Teilchen aus unvernetztem linearen Polyethylen mit niedriger Dichte
EP0924244A3 (de) * 1997-12-15 2000-05-17 Kaneka Corporation Vorgeschäumte Teilchen aus unvernetztem linearen Polyethylen mit niedriger Dichte
WO2020000336A1 (en) * 2018-06-29 2020-01-02 Dow Global Technologies Llc Compositions suitable for manufacturing polyethylene foam, and articles thereof

Also Published As

Publication number Publication date
KR0133478B1 (ko) 1998-04-21
TW307784B (de) 1997-06-11
JP3279382B2 (ja) 2002-04-30
EP0616005B1 (de) 1998-02-18
DE69408548D1 (de) 1998-03-26
KR940021635A (ko) 1994-10-19
DE69408548T2 (de) 1998-08-27
JPH06271701A (ja) 1994-09-27
US5459169A (en) 1995-10-17
CA2118851A1 (en) 1994-09-18

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